Compositions and solutions for use in dyeing and textile printing



Patented, Feb. 27, 1934 COMPOSITIONS AND SOLUTIONS FOR USE IN DYEING AND TEXTILE PRINTING Mordecai Mendoza, West Didsbury, and Arthur George Murray, Whitefield, England, assignors to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Application April 25, 1932, Serial No. 607,494, and in Great Britain May 1, 1931 12 Claims. (Cl. 8-6) This invention relates to the production of dry composition for example, an acid salt, e. g. dry compositions for use in dyeing and textile sodium hydrogen sulphate, may be added, but printing processes and to the production of soluwhen the dry composition is to be stored, the tions therefrom. advantages of adding an acid salt are outweighed According'to the invention we obtain dry comby the disadvantages of susceptibility to moisture o positions for use in dyeing and textile printing and need for special containers. by incorporating in the dry state an N-sul- It is noteworthy that the compounds obtained phonic acid obtainable by the action of a water by the action of sulphites on diazonium comsoluble sulphite on a diazonium compound, with P ds a e read y b e in Water. moreover, 10 or without subsequent reduction, and a comthey undergo no decomp W moderate 65 pound or mixture. which. in an acidified aqueous heat is applied. The dry compositions obtained solution, possesses oxidizing properties. Further, in accordance with our invention are thus readily according to the invention we obtain solutions dis ved n Wa r d by Simple addition of directly applicable in dyeing and textile printing acid (if necessary because an acid salt has not processes and particularly applicable to the probeen added) to the aqueous solution a diazosolu- 7o duction of dyeings by the ice-colour process tion is obtained. The dry compositions produced using arylamides of 2:3-hydroxynaphthoic acid in accordance with the invention can be readily or diacetoacetyldiamines. stored, provided that they contain no acid salt It is known that when diazonium compounds as indicated above, and are eminently suitable are treated with sodium sulphite or ammonium r use n tropicaLOOuntrieS- sulphite or other water-soluble sulphite in aque- The invention is illustrated but notlimited by ous solution there are formed, according to the following examples i Which the parts are conditions, diazonium sulphonic acids or aryly hydrazine-afi-disulphonic acids (see Gattermann, Example 1 Die Praxis des organischen Chemikers, edited by o Wieland, 21st. Edition, Berlin 1928, page 2'19; The 0f the hammum commune so Houben. Die Methoden der organischen Chemie, tamed in f m-anner nor-n 1925, vol. IL page Davies Journal of the parts of 5-ch oro-oo uidme is added with stir- Chemical Society 1922 3.21 page'715' Bamberger ring to so1utl9n of 160 parts of potasslum Suland Meyerberg, Berichte der deutschen chemphlte (ESQ?) m of water F temischen Gesellschaft 1897 30 370' and it is fur- Demure durmg addltlol? kept bekw and ther known that bymfldreduction e g by addi the reaction is maintained slightly alkaline to tion of zinc dustto their aqueous solutions, these fi paper i g .sodlun-a g i g igf' compounds are converted into a u-ary1hydrazine 1e Su (ma 8 1S'pre.c1p1 e m e 35 fiphonic acids. t is also known that when form of a bright yellow crystalline mass WhlCh 9o arylhydrazines are treated with potassium pyrogigg g gg fi gg some hours is filtered sulphate the same u-arylhydraZine-{i-sulphonic acids are obtained (Fischer, Liebigs Annalen, vol. A compqsltlon prepared by i g 22 g; 190, page 97). The compounds, the use of which I of the dned dlagomum gulp, 8

40 is contemplated in the invention, are such comparts of dry potassmm bromlde and 8 pounds as may be obtained eventually by these i i 5KBr+KBrO3 i parts. of acld a' processes from arylamines devoid of hydroxylor i on dl ssolv.lng thls composltlqn sulphonic or carboxylic acid groups. The com- H} p q i dfiazotlzeg 'igt g'g' gfi" pounds or mixtures which possess oxidizing propgigg j gg g g gg fi gg g f 5 erties in an acidified aqueous solution are for example, the soluble persulphates, the soluble Ex m Z6 2 perborates, the soluble bromates or mixtures of a p alkali bromides and alkali bromates or of alkali 152 parts of 3-nitro-4-toluidine are diazotized chlorides and alkali chlorates. Generally we in the usual manner and the diazo solution is 50 11nd that such compounds or mixtures as will on added below 10 C. with stirring to a solution contact with hydrogen halide in aqueous soluof 480 parts of potassium sulphite in about 1,200 tion generate free halogen are particularly suitparts of water. The reaction mixture is kept' able. slightly alkaline by addition of sodium bicar- The substances necessary for generating an bonate as necessary. A partial precipitation of 55 acidified aqueous solution may be present in the yellow crystals occurs during the addition. The

mixture is then heated to 70 C. for about 2 hours and the solution so obtained is then concentrated until crystallization begins. It is then cooled and the yellow crystalline mass which separates is filtered oil and dried. The dry material is ground with 120 parts of potassium bromate to give a dry composition.

On dissolving the composition in water and acidifying the solution with hydrochloric acid a diazo solution is obtained which may be used for preparing azo dyestufis.

Example 3 A diazonium sulphonate paste, obtained as described in Example 1 but not dried is thinned down by adding 2000 parts of cold water; 300 parts of glacial acetic acid are added and the compound is reduced by stirring for about hours with 400 parts of zinc dust. a-(4-chloro-6- 141.5 parts of 5-chloro-o-toluidine are diazotized in the usual manner and the diazo solution is added below 10 C. with stirring to a solution of 2112 parts of crystalline sodium sulphite in about 3000 parts of water. The reaction mixture is kept slightly alkaline by addition of sodium bicarbonate as necessary. The mixture is allowed to stir until the yellow crystalline substance first formed dissolves completely. The operation requires about-200 hours for completion. The solution is filtered and evaporated until crystallization commences. The colourless crystalline product obtained on cooling and consisting of crude 5-chloro-o-tolyl-hydrazine-u-B-disulphonate is filtered off and separated from excess sodium sulphite by fractional crystallization from water. 361 parts of the dried 5-chloro-o-tolylhydrazine-a-fi-disulphonate are then ground with 120 parts of potassium bromate to give a dry composition.

On dissolving the composition in Water and acidifying the solution with hydrochloric acid a solution of the diazonium compound is obtained which may be used for preparing azo dyestuffs.

Example 5 152 parts of m-nitro-p-toluidine are diazotized in the usual manner and the diazo solution is add-.

ed below 10 C., with stirring, to a solution of 252 parts of crystalline sodium sulphite in about 500 parts of water, the reaction mixture being kept slightly alkaline by the addition of sodium carbonate as necessary. The resulting solution is allowed to stir until the diazo compound has disappeared and then saturated with salt. The yellow crystalline compound which separates is filtered off and dried.

267 parts of the dry sulphonate are ground with 55.7 parts of potassium bromate to give a dry composition.

10 parts of the so-obtained composition are dissolved in 200 parts of water and 4.3 parts of hydrochloric acid (32 Tw.) added to the solution. After stirring for 15 to 20 minutes development of the diazo compound is complete and the solution can be bulked to any suitable volume.

Erample 6 2451 parts of dianisidine are diazotized in the usual manner and the diazo solution is added below 10 C. with stirring, to a solution of 500 parts of crystalline sodium sulphite in about 1200 parts of water, the reaction mixture being kept slightly alkaline by the addition of sodium carbonate as necessary. The diazosulphonate separates immediately and after stirring until the diazo-compound has disappeared it is filtered oil and dried.

474 parts of the dry diazosulphonate are ground with 111.4 parts of potassium bromate to give a dry composition.

10. parts of the so-obtained dry composition are suspended in 200 parts of water and 4.3 parts of hydrochloric acid (32 Tw.) added. After stirring for 15 to 20 minutes development of the diazo compound is complete and the solution can be bulked to any volume'suitable for the manufacture of azo dyestuffs.v

Example 7 7 256.5 parts of the diazosulphonate are ground with 55.7 parts of potassium bromate and 495 parts of sodium sulphate to give a dry composition.

'10 parts of the mixture prepared as described in Example 6 are suspended in 66 parts of water and 2.9 parts of hydrochloric acid (32 Tw.) added. After stirring for 15 to 20 minutes development of the diazo compound is complete and the solution may be bulked to any volume suitable for the manufacture of azo dyestuifs.

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that we do not limit ourselves to the specific embodiments thereof except as defined in the appended claims.

We claim:

1. As a new composition of matter a dry mixture comprising an N-sulphonic acid, selected from the group consisting of aryldiazonium sulphonic acids, arylhydrazine-mdisulphonic acids and a-arylhydrazine-B-sulphonic acids, derived from arylamines free from hydroxyl, sulphonic or carboxylic acid groups, together with an agent which in acidified aqueous solution has oxidizing properties.

2. As a new composition of matter a dry mixture as claimed in claim 1 together with an acid salt.

3. As a new composition of matter a dry mixture as claimed in claim 1 together with an alkali metal hydrogen sulphate.

4. As a new composition of matter a dry mixture as claimed in claim 1 together with sodium hydrogen sulphate.

5. As a new composition of matter a dry mixture as claimed in claim 1, in which the agent having in acidified aqueous solution oxidizing properties is a mixture of a water-soluble bromate and a water-soluble bromide.

6. As a new composition 01. matter a dry mixture as claimed in claim 1, in which the agent having in acidified aqueous solution oxidizing properties is a mixture of a water-soluble bromate and a water-soluble bromide, an acid salt being also present.

7. As a new composition of matter' a dry mixture as claimed in claim 1, in which the agent having in acidified aqueous solution oxidizing properties is a mixture of a water-soluble bromate and a water-soluble bromide, sodium hydrogen sulphate being also present.

8. As a new composition of matter a dry mixture as claimed in claim 1, .in which the agent having in acidified aqueous solution oxidizing properties is a water-soluble bromate.

9. As a new composition of matter a dry mix- CHI in which Me represents a metal ion.

11. As a new composition of-a matter a dry mixture as claimed in claim 10 together with an acid salt.

12. 'As a new composition of matter a dry -mixture as claimed in claim 10 together with sodium hydrogen sulphate.

MORDECAI MENDOZA. ARTHUR GEORGE MURRAY. 

